Process for making metallic pattern effects on sheet material



F. LORENZ March 5, 1963 PROCESS FOR MAKING METALLIC PATTERN EFFECTS ON SHEET MATERIAL Filed May 15, 1958 53 lo S' INVENTOR Fel TZ Loes/vz B Y i a... Ik,

3,030,279 PROCESS FORMAKHNG METALLIC PATTERN EFFECTS GN SHEET MATERIAL Fritz Lorenz,'Wattwil, Switzerland, assignor to Heberiein Patent Corporation, New York, NX., a corporation of New York Fiied May 13, 1958, Ser. No. 735,665 Claims priority, application Austria May 14, 1957 3 Claims. (Cl. 15o- 233) -AThis invention relates to a process for producing pattern effectsl on sheet material, and to the resulting product.

The principal object of the invention is to provide a simple, eicient process for producing such pattern effects, and to provide new and useful products thereby.

In carrying out the process in accordance with the invention I join by adhesion a removable continuous coating such as a vacuum vaporized metal on a carrier or support to a'sheet material, for example a fabric. The sheet has a pattern of adhesive which is non-continuous (see for example FIG. 6 of the drawings) thereon. l then separate the sheet and coated carrier whereby the coating adheres to the adhesive. I thus produce a patterned sheet with metal or lustrous metal or other coating material.

r`rlhe carrier may be constituted of various materials ,described more particularly below, and in order to reduce the adherence of the removable coating thereto may be previously coatedewith a liquid of low volatility. Such liquid may'be-a'silicone oil lwhich will remain on the face l-of the coated design attached to the fabric as described below. The adhesive applied as a pattern to the Vfabric Lor the like maybe applied from solution or otherwise. `The carrier containing the vaporized metal coating is joined to the sheet with its adhesive pattern by assembling -the carrier land sheet vone on top of the other and then passing them througha heated calender. The calender is Vheated to a temperature which renders the adhesive sticky 1 ndcauses the metalcoating to adhere to the adhesive -where the two come vin contact.

Instead of metal alone I may employ a color lake and metal, as described more particularly below.

uAfter passing through the calender the fabric and coated carrier are separated, whereby the metal coating of the carrier becomes disengaged from the carrier and adheres Vtothe adhesive pattern onvthe fabric.

The resulting product is a coated patterned fabric or sheet, where the metal or other coating is held in place by the adhesive used for forming the pattern.

Ascarrier material, lsheets or foils of cellulose derivatives areextremely well suited, such as cellulose acetate 'or butyrate,'regenerated cellulose such as viscose, fully synthetic materials such as -polyvinylchloride or-acetate, polyamides such as polyhexamethylene adipamide, polyesters such as polyethyleneglycol terephthalate, poly 'ethylene,vor rubber. Also paper preferably impregnated or coated on one or both sides with plastic material such as polyvinylidene chloride may be used.

As metals to be vaporized onto the carrier aluminum is YveryA well suited; also copper, silver or gold, or alloys such as'copper-alurninum alloys. The carrier can also `be metalyli-zed with several metals successively, for instance first with gold, then with aluminum.

As adhesives to be applied to the she'et material l may use alkylatedphenol resins in benzines with a boiling point VVof between 120 and 160 C., with or without the addition of solutions of acrylonitrile-butadiene-copolymers in methylethylketone. The sheet or foil material, to which the adhesive has been applied, is then dried. When the carrier is laid` onto the material the adhesive is rendered sticky by heat treatment. These adhesives can be applied as such, or in mixture with polysocyanates, preferably :prefer to practice it.

sesamo Patented Mar. 5, 1963 blocked with malonic acid ester, acetoacetic acid ester, or acetylacetone. The heat treatment can thus take place Without previous splitting or` the blocked isocyanates. Such splitting'off can occur immediately after coating the carrier or at any time, at temperatures at least 10 C. above ythe temperature employed for rendering sticky the adhesive.

Furthermore, suitable adhesives include polyvinylethers, the ether group of which contains at least 2 and not more than 8 carbon atoms, as for example, ethyl, propyl, or 'isopropylethen Also, solutions or dispersion of polyvinylacetate as such, or mixed with isocyanates, preferably polyisocyanates in the free state or blocked with lmalonic acid ester, phenols, etc., may be used. lf polyvinylethers or polyvinylesters are used, no drying or heat treatment is necessary. In all cases a carriermay be applied to the sheet material while the adhesive is still moist, i.e. without intermediate drying of the adhesive printed sheet material.

The process of this invention is suitable for the manufacture of lustrous metal ecects on various sheet materials, mainly on textile fabrics, leather, paper and the like. As textile fabrics I may use woven and knitted fabrics, unwoven fabrics either pressed or glued, of natural or regenerated cellulose, cellulose derivatives, animal fibers, synthetic organic polymers such as polyamides, polyesters, or polyvinyl material such as polyacrylonitrile.

Furthermore, I have found that it is of advantage to apply to the carrier a substance of low volatility reducing the adherence of the coating (metal, color lacquer) such as glycerine, glycerine substitute (sorbitol), polyglycol derivatives such as Glyecine (Reg. trademark) paran voil and the like, before application of the coating thereto.

Furthermore, substances may be used which reduce the .adherence of the coating but at the same time act as `-a surface protection of the coating applied t0 the sheet material, by being partially transferred with the vcoating from the carrier onto the fabric. For this, I may use silicone oils, or linseed oil, which after oxidationv produces 'apro- `tective film. Oil reactive resins,such as phenol resins with or without addition of isocyanates, which will form a protectiveiilrn after the heat treatment, may also be used.

Wherecolor lakes are employed they are applied to the carrier before the application of the metal. Theyconsist of colors dissolved in organic solvents anda film-forming component such as cellulose derivatives, as for instance Lcellulose acetate or nitrocellulose or synthetic resins, for instance polyvinyl ether and polyvinyl vester dissolved in organic solvents.

The metal to be applied to the carrier -givesto the color efect the desired luster, but does not 'itself otherwise noticeably appear. Aluminum is especially suitable, but any Yothermetal may of course be used.

The following are examples of the process as I now It is to be understood that these examples are illustrative, and that the invention is not to rbe considered as restricted thereto, except as indicated in adhesive regains its stickiness, so that the aluminum adheres on the portions treated with the `adhesive when the foil is removed. The sheet material is then -washed cold and dried.

Example 2.;Nylontoile is printed on a roller printer with pigment colors and in the same register last printed `printed with the adhesive. and metal adhere to the fabric which subsequently is in a pattern of spots with an adhesive consisting of a polyvinyl acetate dispersion. Without prior drying, a carrier having a vaporized metal coating like that of Example 1 is applied by means of a cold calendar to the treated fabric. As carrier a polyester foil such as a polyethylene glycol terephthalate foil is used, which has been treated with a silicone oil such as D.C. Mold Release Fluid manufactured by Dow Corning Co. in order to reduce the adherence of the metal lm, and then is metallized in a high vacuum rst with a thin coating of gold and then with aluminum. Upon removal of the foil, the metal coating adheres to the spots printed with fthe adhesive, whereby the slight gold-aluminum covering is protected with a thin film of silicone oil. The fabric is then heated to approximately 120 C. for 20 minutes, for the purpose of drying the adhesive.

Example 3.--A wool muslin is printed on a roller printer with pigment colors, and in the same register last 'printed in a pattern with an adhesive consisting of a solution of an alkylated phenol resin in benzine with an kaddition of blocked isocyanates. To the treated and dried fabric, a foil of rigid polyvinyl chloride is applied by means of a calendar heated to 180 C., such foil having been coated in a high vacuum with a lm of a vaporized copper-aluminum alloy of about -4--10-3 mm. thickness, whereby the adhesive is rendered sticky through heat influence. Upon removal of the foil, the gold-colcred metal film adheres on the spots previously printed with adhesive. In order to improve the fastness of the metal effects, the fabric is heated to approximately 200 C. for 20 minutes.

Example 4.-A dyed cotton satin fabric is printed locally in a pattern on a roller printing machine with an adhesive consisting of `a polyvinylacetate dispersion, and is then dried. A foil of regenerated cellulose (viscose) which (by means of a machine for overall application of lake) has been covered with a thin golden yellow color lacquer consisting of Orasol yellow 3 GW, Color Index 18820, manufactured by Ciba Ltd., cellulose acetate, and

"a mixture of organic solvents, and is then metallized in ya high vacuum with aluminum to produce a metal lm of about 10*4103 mm. thickness. The so-treated carrier is caused to adhere to the fabric by passing same -through a calendar heated to a temperature of 80-150 C. Through the heat influence, the adhesive is rendered sticky so that upon removal of the foil the color lake and the aluminum adhere to the parts printed with the adhesive.` One obtains, therefore, very lustrous gold patterns on the predyed fabric base.

Example 5.--A predyed nylon toile is locally printed in a pattern with an adhesive consisting of a solution of an alkylated phenol resin in benzine. A paper sheet is covered by means of a machine in its entire length with three different colored lacquer coatings of 1/3 of the width each, consisting of Sudan Red 3R manufactured by Farbenfabrik Wolfen (Germany) Color Index 21260.

Oil Green 4B manufactured by General Dyestu Co.

Color Index 61565.

Orasol yellow 3GW manufactured by Ciba Ltd. C0101` Index 18,820.

respectively mixed with nitrocellulose, a mixture of acetone and toluene and dioctyl phthalate as a softener. 'Ihe so-treated paper is then metallized with aluminum in a high vacuum to produce a metal lm Iof about 10-4-103 mm. thickness and is applied by means of a heated calender at 60-150 C. to the sheet material previously Upon removal, color lake washed cold and dried. One obtains three-colored patterns of a metallic luster on the predyed fabric.

Example 6.Cottonpercale is pattern printed on a roller printing machine with pigment colors and is provided in the same register with color effects of a metallic luster. These latter effects are obtained with the aid of a carrier of three polyester foils such as polyethylene glycol terephthalate foils covered with lakes of dierent colors, consisting of red, green and blue color solids, a polyvinyl resin, and organic solvents, and then are metallized with copper in a high vacuum to form a metal film of about lO-i-lU*a mm. thickness. A printing machine with nine rollers is used, which rollers are arranged around the pressure cylinder in a manner such that with the irst three rollers of the register three pigment colors, for instance yellow, orange and black, are printed in the same register on the fabric which then runs through a short drying section consisting of infrared tubes, Then, by means of the following six rollers, alternately, the adhesive of a polyvinylacryl resin dispersion is printed patternwise, and then the polyester foil with the respective color lake is pressed on the fabric and then again removed, leaving the fabric with the lustreous colored pattern.

In the accompanying drawing forming part of this application:

FIG. 1 is a diagrammatic showing of means for applying an adhesive coating in pattern, followed by application of a metal thereto for the production of a fabric with a metal pattern thereon.

FIG. 2 is a greatly enlarged detail cross-section of a fabric having adhesive applied to the under surface thereof prior to being brought in contact with the carrier supporting the vaporized metal.

FIG. 3 is a similar view to FIG. 2, showing a section of the fabric in perspective after contact thereof with the metal.

FIG. 4 is a similar view to FIG. 2, but showing adhesive designs on the lower face of the fabric just before contact of same with the carrier containing a color lacquer and metal.

FIG. 5 corresponds to FIG. 4, showing the fabric and adhesive brought in contact with the metal and color lacquer supported by the carrier; and

FIG. 6 is a similar view to FIG. 5, showing the fabric with the lustrous pattern after removal from the carrier.

In FIGS. 2 to 6 the thickness of the dots has been lgreatly exaggerated to show the construction thereof.

Actually the dots, as well as other patterns as produced by the process, are substantially Hush with the surface of the fabric.

Referring now to FIG. 1 of these drawings, the numeral 1 designates a roll of fabric or like material. The fabric passes through rollers 2 which apply adhesive fromi the trough 3 in pattern thereon. The fabric so patternedV then passes between calender rollers 4 where it meets the carrier 5. This carrier, consisting of sheets of foil or cellulose acetate or any of various other substances ref' ferred to above, after having been coated and dried by means of dryer 16 containing infrared tubes passes through the vacuum chamber 6 where aluminum or other metal is vaporize'd from the electrically heated trough 15" and deposited thereon, as hereinabove described. Where a color lacquer is to be applied prior to the deposition of such metal, it may be applied from a solution thereof contained in a trough 7 containing a roller 8 provided with a doctor blade 14 which deposits the lacquer on the surface of the ycarrier 5. The carrier with the metal coating, with or without the color lacquer, then passes to the calendar rollers 4 where the patterned adhesive comes in contact with the metal. As the fabric with the patternwise applied adhesive passes along, the metal is removed from the carrier. If the carrier also has a coating of color lacquer, it will adhere with the metal to the adhesive pattern on the fabric. The patterned fabric containing the metal, with or without the color lacquer is then wound on roller 9. The carrier separated from the fabric is wound up on roller 10.

Referring now to FIG. 2, the fabric is there shown containing circular dots of adhesive 11 applied thereto by roller 2. Beneath the fabric is the carrier 5 with metal coating 12 thereon. The adhesive patterned fabric is then brought in contact with the metal coating 12 held on the carrier, and when these two are passed through the heated calender rollers 4 and then separated, the result is as shown in FIG. 3. The fabric 1 has the dots of adhesive 11 covered by corresponding metal portions 12.

In FIGS. 4 to 6 is shown a similar process where a color lacquer and metal are employed. In FIG. 4 the fabric 1 is shown as coated with dots of adhesive 11, and beneath this fabric is the carrier 5 containing a coating 13 of a color lacquer, above which is the coating of metal 12. The fabric pattern printed with the adhesive is shown as brought together with the carrier containing the color lacquer and metal in FIG. 5, as it would appear in passing through the lheated calender rollers 4. In FIG. 6 the fabric has been separated from the carrier showing dots consisting of successive layers of adhesive, metal and co-lor lacquer. ",Depressions in the form of dots occur in the carrier assembly.

I claim:

l. A process of applying a lustrous metallic Pattern to fabric, which comprises vacuum depositing a continuous film of metal on a support, applying a desired non-contionuous pattern of adhesive to a fabric, heating the adhesive tofrender it sticky, contacting the film of metal with the patterned adhesive, and separating the fabric and support whereby that portion of the metal film contacted by the patterned adhesive becomes disengaged from the support and is transferred from the support and becomes adherent tothe fabric to produce a metal patterned fabric.

2. A process of applying a lustrous metallic pattern to fabric, which comprises vacuum depositing a continuous film of metal on a support coated with a liquid of low volatility to reduce the adherence of the metal to the carrier, applying a desired non-continuous pattern of adhesive to a fabric, heating the adhesive to render it sticky, contacting the film of metal with the patterned adhesive, and separating the fabric and lsupport whereby that portion of the metal film contacted by the patterned adhesive becomes disengaged from the support and is transferred from the support and becomes adherent to the fabric to produce a metal patterned effect.

3. A process of applying a metallic pattern to fabric, which comprises coating a support with a removable color lacquervacuum depositing a continuous film of metal on top of said lacquer, applying a desired non-continuous pattern of adhesive to a fabric, heating the adhesive to render it sticky, contacting the film of metal and lacquer with the patterned adhesive, and separating the fabric and support, whereby that portion of the metal film con tacted bythe patterned adhesive becomes disengaged from the support and is transferred, together with the color lacquer from the support, and becomes adherentrto the fabric to produce a metal and color patterned fabric.

References Cited in the file of this patent UNITED STATES PATENTS 2,360,515 Ormond Oct. 17, 1944 2,597,396 Squires May 20, 1952 2,638,428 Gordon et al May 12, 1953 2,700,629 Townsend Ian. 25, 1955 2,703,772 Keithly Mar. 8, 1955 2,872,340 Newman et al Feb. 3, 1959 FOREIGN PATENTS 528,142 Canada July 24, 1956 OTHER REFERENCES Vacuum Deposition of Thin Films by L. Holland, publ. in 1950 by John Wiley & Sons, Inc., N Y., pages 207-8, 220. 

1. A PROCESS OF APPLYING A LUSTROUS METALLIC PATTERN TO FABRIC, WHICH COMPRISES VACUUM DEPOSITION A CONTINUOUS FILM OF METAL ON A SUPPORT, APPLYING A DESIRED NON-CONTINUOUS PATTERN OF ADHESIVE TO A FABRIC, HEATING THE ADHESIVE TO TENDER IT STICKY, CONTACTING THE FILM OF METAL WITH THE PATTERNED ADHESIVE, AND SEPARATING THE FABRIC AND SUPPORT WHEREBY THAT PORTION OF THE METAL FILM CONTACTED BY THE PATTERNED ADHESIVE BECOMES DISENGAGED FROM THE SUPPORT AND IS TRANSFERRED FROM THE SUPPORT AND BECOMES ADHERENT TO THE FABRIC TO PRODUCE A METAL PATTERNED FABRIC. 